U.S. patent application number 10/200877 was filed with the patent office on 2004-03-25 for enhanced polymerization process.
This patent application is currently assigned to General Electric Company. Invention is credited to Colborn, Robert E., Feng, Ke, Ferraris, Dane M., Littlejohn, Matthew Hal, Lowry, Vern, Townsend, David Francis, Vilasagar, Shripathy.
Application Number | 20040059079 10/200877 |
Document ID | / |
Family ID | 26896191 |
Filed Date | 2004-03-25 |
United States Patent
Application |
20040059079 |
Kind Code |
A1 |
Vilasagar, Shripathy ; et
al. |
March 25, 2004 |
Enhanced polymerization process
Abstract
An emulsion polymerization process for the preparation of
polybutadiene grafted with styrene and acrylonitrile monomers in a
reaction system is provided. The resultant product has a low end
content of unreacted residual monomers, low yellowness index, and
improved impact strength. The diene rubber is prepared via a
process wherein a chain transfer agent is added on a continuous
basis to give a rubber substrate having a low crosslink density. In
one embodiment of the invention, the process includes charging the
reaction system with a pre-selected diene emulsion with a low
crosslink density, adding a first portion of at least one of a
styrene monomer and acrylonitrile monomer to the diene emulsion,
adding to the reaction system, over a predetermined time, an
initiator and a second portion of acrylonitrile and styrene
monomer, and polymerizing the catalyzed reaction mixture of diene
substrate, styrene and acrylonitrile to form ABS graft polymers. In
another embodiment, a third monomer is added after the conversion
rate of the monomers is greater than 98%.
Inventors: |
Vilasagar, Shripathy;
(Parkersburg, WV) ; Lowry, Vern; (Ottawa, IL)
; Ferraris, Dane M.; (Parkersburg, WV) ; Feng,
Ke; (Vienna, WV) ; Colborn, Robert E.;
(Niskayuna, NY) ; Littlejohn, Matthew Hal; (Green
Island, NY) ; Townsend, David Francis; (Loganville,
GA) |
Correspondence
Address: |
Hanh T. Pham
GE Plastics
One Plastics Avenue
Pittsfield
MA
01201
US
|
Assignee: |
General Electric Company
|
Family ID: |
26896191 |
Appl. No.: |
10/200877 |
Filed: |
July 23, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60307445 |
Jul 24, 2001 |
|
|
|
Current U.S.
Class: |
526/335 |
Current CPC
Class: |
C08F 36/04 20130101;
C08F 2/38 20130101; C08F 279/04 20130101; C08F 2/38 20130101; C08F
36/04 20130101 |
Class at
Publication: |
526/335 |
International
Class: |
C08F 036/00 |
Claims
What is claimed is:
1. A semi-batch process for preparing diene rubber latex, said
process comprising: adding an initial liquid batch to a reaction
system, said batch being of sufficient volume to fill the reactor
to about 40% to about 80% volume, said batch comprising water, an
emulsifier, and a diene monomer, adding a liquid feed composition
continuously to the reactor at or after the conclusion of the
addition of the liquid batch to the reaction system, said liquid
composition comprising a diene monomer, an initiator and a chain
transfer agent, and reacting said composition to prepare a diene
rubber latex.
2. The process of claim 1, wherein the chain transfer agent is
continuously added at a controlled rate to the reaction system.
3. The process of claim 1, wherein said diene rubber latex has a
cross link density (% A) from about 10 to about 60.
4. The process of claim 3, wherein said diene rubber latex has a
cross link density (% A) from about 24 to about 44.
5. The process of claim 1, wherein said initial liquid batch
further comprises a co-monomer and said liquid feed composition
further comprises a co-monomer.
6. The process of claim 5, wherein said co-monomer is selected from
styrene, acrylonitrile, and methyl methacrylate.
7. The process of claim 1, wherein said initial liquid batch
further contains a chain transfer agent.
8. The process of claim 1, wherein the temperature of the reaction
system ranges from about 120.degree. F. to about 185.degree. F.
9. The process of claim 1 wherein the chain transfer agent
comprises at least one of C.sub.1-C.sub.15 alkyl mercaptans,
n-dodecyl mercaptans, i-dodecyl mercaptans and t-dodecyl
mercaptans.
10. The process of claim 1, wherein the total amount of chain
transfer agent added is from about 0.1 to about 3 weight parts per
100 weight parts of the diene monomer.
11. A method of optimizing the impact strength of an ABS graft
polymer product while achieving higher conversion and reduced
monomer emissions in preparing said ABS graft polymer product, by
offsetting an increase in crosslink density % A in said ABS graft
polymer with a selection of a diene substrate having a low
crosslink density % A to prepare said ABS graft polymer.
12. A method of optimizing the impact strength of an ABS graft
polymer, said method comprising: correlating rubber crosslink
density % A data of diene substrates used to make said ABS graft
polymer with a low temperature impact strength data of ABS graft
polymers made therefrom; and selecting the appropriate crosslink
density % A of the diene substrates associated with the desired
impact strength for use in a subsequent graft reaction.
13. A process to prepare ABS graft polymers having an improved
impact strength, said method comprising: preparing a diene rubber
latex via a semi-batch process wherein a chain transfer agent is
added to said process on a continuous basis for said diene
substrate to have an appropriate crosslink density % A to achieve a
desired impact strength; charging a reaction system with said diene
rubber latex; adding to the reaction system, over a predetermined
time, acrylonitrile and styrene monomers and optionally, an
initiator; and polymerizing said reaction mixture of polybutadiene,
styrene and acrylonitrile.
14. The process of claim 13, further comprising adding a third
monomer to the reaction mixture after at least 95% of said styrene
and acrylonitrile monomers have reacted.
15. The process of claim 14, further comprising adding a third
monomer to the reaction mixture after at least 98% of said styrene
and acrylonitrile monomers have reacted.
16. The process of claim 15, further comprising adding a third
monomer to the reaction mixture after at least 99% of said styrene
and acrylonitrile monomers have reacted.
17. A process to prepare ABS graft polymers having a low end
content of unreacted residual monomers, said process comprising:
charging a reaction system with a diene emulsion; adding to the
reaction system, over a predetermined time, acrylonitrile and
styrene monomers and optionally, an initiator; polymerizing the
reaction mixture of polybutadiene, styrene and acrylonitrile; and
adding a third monomer to the reaction mixture after at least 98%
of said styrene and acrylonitrile monomers have reacted.
18. The process of claim 17, further comprising adding at least an
initiator along with said third monomer to the reaction
mixture.
19. The process of claim 17, wherein the initiator comprises at
least one of cumene hydroperoxide, sodium persulfate, potassium
persulfate, ammonium persulfate, di-isopropylbenzene hydroperoxide,
and tertbutyl-peroxide.
20. The process of claim 17, wherein said third monomer is added to
the reaction mixture after at least 99% of said styrene and
acrylonitrile monomers have reacted.
21. An emulsion polymerization process for the preparation of diene
grafted with styrene and acrylonitrile monomers in a reaction
system to form grafted ABS polymers having a low end content of
unreacted residual monomers and an improved impact strength, said
process comprising: charging the reaction system with an emulsion
comprising a diene substrate having a crosslink density % A which
has been selected based on a desired impact strength of an ABS
graft polymer product; adding a first portion of at least one of
styrene monomer and acrylonitrile monomer to the diene emulsion;
polymerizing said reaction mixture of diene, styrene and
acrylonitrile; and adding a third monomer to the reaction mixture
after at least 95% of said styrene and acrylonitrile monomers have
reacted.
22. The process of claim 21, wherein said third monomer is added to
the reaction mixture after at least 98% of said styrene and
acrylonitrile monomers have reacted.
23. The process of claim 22, wherein said third monomer is added to
the reaction mixture after at least 99% of said styrene and
acrylonitrile monomers have reacted.
24. The process of claim 21, wherein the third monomer is added at
an amount of about 0.5 to about 5.0 parts of the third monomer per
100 parts of polymer and monomer.
25. The process of claim 21, wherein the third monomer comprises at
least one of methyl acrylate, ethyl acrylate, butyl acrylate,
2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate,
isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butyl
methacrylate, isobornyl methacrylate, isodecyl methacrylate,
cyclohexyl methacrylate, benzyl methacrylate, acrylamide,
methacrylamide, vinylidine chloride, vinylidine bromide, vinyl
acetate, vinyl propionate, dimethyl maleate, diethyl maleate,
dibutyl maleate, dimethyl fumarate, diethyl fumarate, and dibutyl
fumarate.
26. The process of claim 21, wherein the additional monomer
comprises methyl methacrylate.
27. The process of claim 21, wherein an additional initiator is
added with the third monomer.
28. The process of claim 21, wherein the initiator comprises at
least one of cumene hydroperoxide, sodium persulfate, potassium
persulfate, ammonium persulfate, di-isopropylbenzene hydroperoxide,
and tertbutyl-peroxide.
29. A process for the preparation of diene substrate grafted with
styrene and acrylonitrile monomers in a reaction system for a ABS
graft polymer product having a low yellowness index, said process
comprising: charging the reaction system with a diene emulsion;
adding to the reaction system over a predetermined time, an
initiator, acrylonitrile monomer and styrene monomer, at such a
rate to maintain a level of unreacted styrene monomer to unreacted
acrylonitrile monomer in said reaction system of about 1.5 to 1 to
about 4 to 1; and polymerizing said reaction mixture of diene,
acrylonitrile and styrene.
30. The process of claim 29, wherein the ratio of diene added to
the total of styrene monomer and acrylonitrile monomer added is
about 0.1 to 1 to about 3 to 1.
31. The process of claim 29, further comprising adding a third
monomer to the reaction mixture after least 98% of said styrene and
acrylonitrile monomers have reacted.
32. The process of claim 29, wherein said acrylonitrile monomer and
styrene monomer are added in at least two portions, a first portion
comprising at least one of a styrene monomer and an acrylonitrile
monomer, and a second portion of acrylonitrile and styrene
monomers.
33. The process of claim 29, wherein charging the reaction system
with a diene emulsion comprises charging the reaction system with
an emulsion comprising diene substrate having a crosslink density
which has been selected based on a desired low temperature impact
of a desired ABS graft polymer.
34. The process of claim 29, wherein said reactor system is one of
a batch process, a semi-batch process, or a continuous process.
Description
[0001] THIS APPLICATION CLAIMS RIGHTS OF PRIORITY FORM U.S.
PROVISIONAL PATENT APPLICATION SERIAL No. 60/307,445, ALL FILED
JUL. 24,2001, WHICH ARE HEREBY INCORPORATED BY REFERENCE.
[0002] This invention relates generally to a process for preparing
polymers having a low residual monomer content while retaining
material properties such as flow, impact and color.
BACKGROUND OF THE INVENTION
[0003] In a two-step embodiment to manufacture ABS in a typical
emulsion process, a rubber latex is made in the first step. EPA
762693 discloses the first step of the emulsion process, a
semi-batch process for the manufacture of diene rubber latex
wherein a chain transfer agent such as t-ddm, is added upfront in
the beginning of the reaction with the butadiene monomer and
initiator. In order to get a sufficient low crosslink density in
the rubber latex, high levels of chain transfer agents must be
added with associated raw material costs and problems with reactor
fouling as well as residual odor in final ABS products from the
chain transfer agents.
[0004] In the second step of an emulsion process, acrylonitrile and
styrene may be emulsion polymerized with the diene rubber latex to
form an acrylonitrile-butadiene-styrene (ABS) graft polymer. The
polymerization reaction is typically run to completion. However,
sometimes even when the polymerization is substantially complete,
undesired amounts of acrylonitrile monomer and/or styrene monomer
dissolved or occluded in the polymer and in the reaction system
water can still remain. The normal unit operations of stripping by
vacuum or steam stripping the reaction system content do not remove
all of this undesirable residual acrylonitrile and/or styrene
monomer.
[0005] The importance of monomer conversion in ABS material has
been recognized since its inception as a commercial material. The
acute toxicity of acrylonitrile is well known and both butadiene
and styrene monomers have been associated with health issues. From
a manufacturing perspective, the full utilization of the monomers
provides both for higher productivity and lower costs associated
with recovery, recycle or disposal of the residual monomers. Also,
manufacturers must abide by regulations that apply to their plant
which place limits on allowable volatile material releases. In the
marketplace, there is an increasing desire to deliver ABS material
(e.g., pellets) with low levels of volatile materials.
[0006] There are several processes which are employed to achieve
low residual monomer levels in the ABS product. In many cases, this
is done by drying in ovens or fluid beds after the polymerized
material is isolated. This `end-of-pipe` approach allows for
excellent reduction of the residual monomers, but at the expense of
both investment capital and operating costs to achieve the desired
reduction. A potentially more effective approach entails the more
complete conversion of the monomers during the polymerization
reaction. Even within this avenue, several different methodologies
have been used.
[0007] The use of additional monomers to aid in conversion has been
employed both during the main reaction and at the end of the
grafting reaction. For example, vinyl carboxylates have been used
during the course of the reaction. Other patents describe the use
of additional monomers at the end of the reaction including
butadiene (U.S. Pat. No. 4,272,425), acrylonitrile (U.S. Pat. No.
4,822,858), n-vinyl mercaptans (German Patent No. DE 3,327,190),
and methyl methacrylate (MMA) (U.S. Pat. No. 3,991,136--after
polymerizing at least about 90% of monomer formulation). Most of
the work with additional monomers do include some additional
initiators also. U.S. Pat. No. 4,301,264 describes the use of a
secondary initiator late in the reaction.
[0008] The problem with existing approaches has been that either
the residual monomer levels are still higher than desirable or that
a concomitant loss in other physical properties (e.g., color or
impact strength) makes the resultant material unattractive as a
commercial product.
[0009] As noted above, it is highly desired to lower emission of
volatile hazardous organic components. As the conversion to ABS
graft polymer is increased in such a polymerization to reduce
residual monomers (which ultimately end up as hazardous volatile
organic compounds) at the end of a graft polymerization, the rubber
crosslink density of the graft polymer is also increased which
adversely affects the impact, especially at low (sub zero)
Fahrenheit temperatures.
[0010] In order to improve the low temperature impact, typically in
the past either the graft molecular weight is increased and/or a
higher molecular weight matrix styrene acrylonitrile (SAN) is used.
However, either of these two approaches raise the melt viscosity of
the blend, thus adversely affecting the flow and processability of
the blend. Another approach used is to increase rubber level in the
product formulation, which also reduces flow and reduce
modulus.
BRIEF SUMMARY OF THE INVENTION
[0011] In one embodiment of the invention, a semi-batch process for
preparing low crosslink density diene rubber substrate is provided.
The process includes adding an initial liquid batch to a reaction
system, said liquid batch includes water, an emulsifier, and a
diene monomer. The process further includes adding a liquid feed
composition including butadiene, an initiator and a chain transfer
agent to the reactor system, at or after the conclusion of the
addition of the liquid batch to the reaction system. The continuous
addition of the chain transfer agent allows for the preparation of
a low density cross linked diene rubber substrate.
[0012] In another embodiment, a method of optimizing the flow and
low temperature impact of ABS graft polymers is provided, which
includes associating the rubber crosslink density of diene
substrate used to make ABS graft polymer with the room temperature
and low temperature impact strength of the ABS graft polymer made
therefrom, and selecting the appropriate crosslink density diene
substrate associated with the desired flow and low temperature
impact of the ABS graft polymer.
[0013] In a third embodiment, a method of maintaining the
flow-impact balance in an ABS graft polymer product while achieving
higher conversion and reduced monomer emissions is provided. The
method includes offsetting a crosslink density (% A) increase in
the ABS graft polymer (due to increased conversion) by selecting a
diene substrate of lower crosslink density (% A) to prepare the ABS
graft polymer product.
[0014] In yet another embodiment of the present invention, an
emulsion polymerization process for the preparation of
polybutadiene grafted with styrene and acrylonitrile monomers in a
reaction system is provided. The resultant product has a low end
content of unreacted residual monomers. The process includes: a)
charging the reaction system with a diene emulsion; b) adding to
the reaction system, over a predetermined time, an optional
initiator, acrylonitrile and styrene monomers; c) polymerizing the
catalyzed reaction mixture of polybutadiene, styrene and
acrylonitrile; and d) adding a third monomer and an optional
initiator to the reaction mixture after the conversion rate of the
monomers is about 98% or higher.
[0015] In another embodiment, an emulsion polymerization process
for the preparation of ABS graft polymer having a low yellowness
index is provided. The process includes maintaining an appropriate
ratio of unreacted styrene to acrylonitrile monomers in the
reaction system.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 shows the dependence of rubber crosslink density (%
A) of an ABS graft polymer on rubber crosslink density (% A) of a
substrate.
[0017] FIG. 2 shows the dependence of notched Izod impact at room
temperature on rubber crosslink density (% A) of the ABS graft
polymer.
[0018] FIG. 3 shows the dependence of notched Izod impact at low
temperature (-20.degree. C.) on rubber crosslink density (% A) of
the ABS graft polymer.
[0019] FIG. 4 is an overlay plot showing the optimum crosslink
density of rubber (% A) in a substrate needed for low temperature
(-20C) notched Izod impact, while meeting low NAV requirements.
[0020] FIG. 5 is a plot of the results of a design of experiments
(DOE), showing the correlation of a continuous feed of the chain
transfer agent t-DDM feed with the crosslink density of diene
rubber substrate.
DETAILED DESCRIPTION OF THE INVENTION
[0021] ABS polymers can be produced via emulsion or mass (bulk)
polymerization processes. The emulsion polymerization process is a
two-step process, with the first step to prepare a rubber latex,
and the second step for the polymerization of styrene and
acrylonitrile in the rubber latex solution to form an ABS latex.
The ABS polymer is recovered through coagulation of the ABS latex
by adding a stabilizing agent. The slurry is filtered or
centrifuged to recover the ABS resin.
[0022] Production of low-crosslink density rubber latex via
continuous addition of chain transfer agent. In one embodiment of
an emulsion polymerization process of the present invention, a
low-crosslink density rubber latex is achieved. Applicants have
surprisingly found that the continuous addition of the chain
transfer agent during the feed portion of the semi-batch process to
make rubber latex allows for the production of low crosslink
density rubber latex, as compared to batch charging the chain
transfer agent (adding all the chain transfer agent at the
beginning of the reaction) in the prior art process.
[0023] In one embodiment of the invention, the rubber latex is a
diene rubber latex. Suitable diene monomer feed includes butadiene
and isoprene and various comonomers, which may be present to
produce copolymers of butadiene with up to 50 percent by weight of
comonomers such as styrene, acrylonitrile, methylmethacrylate or
C.sub.1-C.sub.6-alkylacrylate. In another embodiment, up to 35
percent by weight of comonomers is added.
[0024] Comonomers can be present in the rubber at a level of less
than 50 percent by weight, preferably less than 40 weight percent
and most preferably less than about 25 weight percent based on the
total weight of the monomers. Most preferably no comonomer is used
due generally to the tendency of comonomer to reduce the efficiency
of the reflux cooling. Suitable comonomers include vinyl aromatic
monomers and vinyl cyanide (unsaturated nitrile) monomers.
[0025] Monovinylidene aromatic monomers (vinyl aromatic monomers)
which may be employed include styrene, alpha-methyl styrene,
halostyrenes i.e. dibromostyrene, mono or di alkyl, alkoxy or
hydroxy substitute groups on the nuclear ring of the Monovinylidene
aromatic monomer i.e. vinyl toluene, vinylxylene, butylstyrene,
para-hydroxystyrene or meth-oxystyrene or mixtures thereof. The
monovinylidene aromatic monomers utilized are generically described
by the following formula: 1
[0026] wherein X is selected from the group consisting of hydrogen,
alkyl groups of 1 to 5 carbon atoms, cycloalkyl, aryl, alkaryl,
aralkyl, alkoxy, aryloxy, and halogens. R is selected from the
group consisting of hydrogen, alkyl groups of 1 to 5 carbon atoms
and halogens such as bromine and chlorine. Examples of substituted
vinyl aromatic compounds include styrene, 4-methyistyrene,
3,5-diethylstyrene, 4-n-propylstyrene, .alpha.-methylstyrene,
.alpha.-methyl vinyltoluene, .alpha.-chlorostyrene,
.alpha.-bromostyrene, dichiorostyrene, dibromostyrene,
tetrachiorostyrene mixtures thereof and the like. The preferred
monovinylidene aromatic monomers used are styrene and/or
a-methylstyrene.
[0027] Suitable vinyl cyanide monomers include acrylonitrile and
substituted vinyl cyanides such as methacrylonitrile. The
acrylonitrile and substituted acrylonitrile are described
generically by the following formula: 2
[0028] wherein R.sup.1 may be selected from the same group set out
for R as previously defined. Examples of such monomers include
acrylonitrile, ethacrylonitrile, methacrylonitrile,
.alpha.-chloroacrylonitrile, and .alpha.-bromoacrylonifrile.
[0029] It should be noted that the monomers listed above are useful
in the first step of polymerizing butadiene to make diene rubber
latex, and also in the second step of the emulsion polymerization
process to make ABS graft polymers.
[0030] Chain-transfer agents are added to the emulsion
polymerization systems of the present invention in order to improve
final polymer properties. Chain-transfer agents generally function
as molecular weight modifiers. The chain-transfer agent reacts with
a growing polymer chain to form a "dead" polymer with the
concurrent formation of a new center for polymer growth. Typical
agents are, for example, organic sulphur compounds, such as
C.sub.1-C.sub.15 alkyl mercaptans, n-, i- and t-dodecyl mercaptan
being preferred. It is recognized that the amount of chain-transfer
agent employed will vary based on the particular chain-transfer
agent ("CTA"), the monomer or mixture of monomers employed, the
initiator employed, the polymerization reaction conditions, etc. In
one embodiment, the CTA is added in the range of about 0.1 to 3
weight part of CTA per 100 weight part of the monomer. In a second
embodiment, the amount is about 0.1 to 2 weight part of CTA per 100
weight part of the monomer. In yet a third embodiment, the amount
is about 0.2 to 0.5 weight part.
[0031] In one embodiment, about 10-50% of the chain transfer agents
are added to the initial liquid batch composition, with the rest of
the chain transfer agents being included with the continuous feed
composition. In another embodiment, 100% of the chain transfer
agents are added with the continuous feed.
[0032] Stabilizer and/or emulsifier are also added to the emulsion
polymerization in such a manner that the final particle size of the
finished latex is controlled. Emulsifiers are known and are
commonly used in emulsion polymerization (D. C. Blackley, Emulsion
Polymerization, chapter 7, Applied Science Publishers Ltd., London,
1975).
[0033] Emulsifiers which may be used according to the invention
include the so-called anionic emulsifiers, such as higher fatty
alcohol sulphates, higher alkyl sulphonates, alkylaryl sulphonates,
aryl sulphonates, together with the condensation products thereof
with formaldehyde, salts of sulphosuccinic acid esters and
sulphated ethylene oxide adducts; the so-called non-ionic
emulsifiers include the known reaction products of ethylene oxide
with fatty alcohols, such as lauryl, myristyl, cetyl, stearyl and
oleyl alcohol, with fatty acids, such as lauric, myristic,
palmitic, stearic and oleic acid, and the amides thereof, and with
alkylphenols, such as isooctyl-, isononyl- and dodecylphenol.
[0034] Emulsifiers are generally used in quantities of 0.1 to 10
wt. % , in particular of 0.2 to 8 wt. % , based on the total
quantity of monomers used.
[0035] Free radical initiators well-known in the art are also
employed in the emulsion process to enhance the reaction rate. The
initiator can be introduced with the feed to maximize the heat
generation rate early in the process. Examples of initiators
include water soluble initiators, such as, for example, peroxygen
compounds, especially inorganic persulfate compounds such as for
example ammonium persulfate, potassium persulfate and sodium
persulfate; peroxides such as for example hydrogen peroxide;
organic hydroperoxides, such as for example cumene hydroperoxide
t-butyl hydroperoxide, acetyl peroxide, lauroyl peroxide; peracetic
acid and perbenzoic acid; redox initiators wherein a water soluble
reducing agent such as a ferrous compound promotes the
decomposition of peroxides, persulfates and the like; as well as
other free radical producing materials such as
2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and
the like. In one embodiment, the initiator is a high activity redox
initiator such as cumene hydroperoxide or other hydroperoxides in
combination with other compounds such as reducing agents, heavy
metal salts and complexing agents. In one embodiment, initiators
are added to provide an initial reaction rate of about at least 10
percent of the total diene of the reaction reacted per hour. In
another embodiment, between 15 and 20 percent.
[0036] A semi-batch process for the production of a diene-based
rubber latex involves: a) providing the reaction system with an
initial liquid batch composition comprising water, emulsifier,
diene monomer, optionally a chain transfer agent, an initiator
and/or co-monomers such as acrylonitrile and styrene, optionally
inorganic and organic salts; b) feeding into the vessel a liquid
feed composition comprising diene monomer and a chain transfer
agent, optionally co-monomers such as acrylonitrile and styrene,
and initiator in which the initiator may be dissolved in water; c)
providing cooling during the continuous feeding; and d) reacting
the diene monomer during and after the continuous feeding. The rate
of feed is such that the level of unreacted diene monomer is
minimized and peak heat generation occurs early in the process.
[0037] In one embodiment, the liquid batch composition also
contains electrolytes, reducing agents, heavy metal salts and
complexing agents. The initial liquid batch composition may contain
from 10 to 30 weight percent of the total weight of diene monomer
used in the process. In one embodiment, from 12 to 28 weight
percent thereof. In another embodiment of the invention, from 15 to
25 weight percent thereof. This low level of initial diene monomer
allows for greater reaction rate control.
[0038] The feed is to supply the remaining diene monomer and chain
transfer agents to the reaction vessel over a period of time and at
a controlled rate. The continuous feed occurs at a rate of between
5 and 20 volume present per hour based on the total volume of the
initial batch liquid composition, and the feeding is completed
during the first 2 to 12 hours of the process. Mixing is done
during the reaction by using a stirrer.
[0039] In one embodiment of the present invention, the continuous
feed composition includes diene monomer and 100% of the total
amount chain transfer agents to be used in the reaction. In a
second embodiment, the continuous feed includes about 80% of the
total amount of chain transfer agents used. In one embodiment, the
feed is controlled to achieve a final liquid volume of at least 80
volume % in the reactor based on the total volume of the reactor,
and a diene monomer conversion of at least 80 wt. % on the total
weight of diene used in the process. In another embodiment, the
final liquid volume is 84 volume % and the diene monomer conversion
is at least 90% based on the total weight of diene used in the
process. In another embodiment, the conversion rate of the diene
monomer is at least about 93% .
[0040] The initial liquid batch composition in to fill the reactor
is about 40% to about 80% of the reactor volume. In one embodiment,
from 50 to 70 % thereof. In another embodiment, from 50 to 60 % .
The volume of the vessel is defined as the internal volume of the
vessel available for occupation by the liquid and vapor containing
diene reactant. The relatively low initial liquid level allows for
a maximization of efficient vapor space cooling; and when utilizing
a high activity initiator in the feed composition, the reaction
rate and heat generation rate can be at a peak early in the process
while the liquid level is relatively low and while the efficient
vapor cooling space is maximized.
[0041] The reaction time of a semi-batch process is typically about
5-20 hours or so, with the reaction temperature ranging from about
120.degree. F. to about 185.degree. F. and preferably from about
135.degree. F. to about 165.degree. F. In one embodiment, the
reaction time of the semi-batch process of the present invention is
about 5 to 15 hrs. In a third embodiment, from about 8 to 12 hrs.
The reactor pressure is typically between 20-150 psig depending on
the reaction temperature. Reaction rate generally peaks during the
first two hours of the reaction when the vapor space is greatest in
the vessel, thereby allowing for the greatest level of vapor space
cooling which is generally more efficient than the liquid space
cooling.
[0042] In one embodiment of the present invention, the latex
viscosity of the rubber latex is no greater than 200 centipoises
(for example, as measured by using Automation Products, Inc. Model
#CL-10 DV3 online viscometer). In another embodiment, it is between
50 and 200 centipoises throughout the reactor.
[0043] In one embodiment, the rubber latex produced has a number
average particle size diameter of between 600 Angstroms and 1200
Angstroms, and has less than 10% by number of particles having
diameters of less than 500 Angstroms. The viscosity of the reaction
liquid is preferably less than 200 centipoises throughout the
reactor.
[0044] In one embodiment of the invention, the final crosslink
density (% A) of the polybutadiene is from about 10 to about 60 and
in another embodiment, about 20 to about 50% . In a third
embodiment, the final crosslink density (% A) of the polybutadiene
is about 24-44% . The rubber crosslink density is represented as %
A, which measurement method can be found in "Pulsed NMR Analysis of
Polybutadiene Emulsion Polymerization Reactions: Preliminary
Evidence for Changes in Cross-Link Density," Donald H. Ellington,
GE Plastics, Bruker Minispec Application Note 36, 1991.
[0045] Delayed Addition of Third Monomer. In the second step of the
emulsion polymerization process to make ABS, monovinylidene
aromatic hydrocarbon monomers (e.g., styrene) and ethylenically
unsaturated nitrile monomers (e.g., acrylonitrile) are polymerized
in the rubber latex to form an ABS polyblend latex. In an example
of a semi-batch process, an initial charge of substrate including
water, surfactant and polybutadiene is made to a reaction system
and at or after the conclusion of the completion of the initial
charge, a pre-soak operation is carried out which include the
addition of at least one of styrene, acrylonitrile or a mixture of
styrene and acrylonitrile.
[0046] Applicants have found that the delay addition of a third
monomer until the monomer conversion is greater than 98%
surprisingly allows for a decrease in the amount of residual
monomers or unreacted styrene NAVs. The conversion rate is based on
the total conversion rate of the monovinylidene aromatic
hydrocarbon monomers and ethylenically unsaturated nitrite
monomers. The resultant ABS product has a low content of unreacted
residual monomers. The delayed addition of a third monomer is
referred herein as a "post-shot" addition. In another embodiment, a
delay addition of an initiator was made in conjunction with the
third monomer.
[0047] The third monomer to be added to the emulsion grafting
reaction after the 98% plus monomer conversion point is selected on
the basis of being highly reactive with the monomer formulation,
including both the monovinylidene aromatic hydrocarbon monomer and
the ethylenically unsaturated nitrile monomer. In one embodiment,
the third monomer is a monomer having a low boiling point below
120.degree. C. so that it can easily volatilized during the
recovery of the polyblend from a latex by coagulation, washing, and
drying.
[0048] The third monomers typically include at least one of methyl
acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
cyclohexyl acrylate, benzyl acrylate, isopropyl acrylate, methyl
methacrylate, ethyl methacrylate, butyl methacrylate, isopropyl
methacrylate, isodecyl methacrylate, cyclohexyl methacrylate,
benzyl methacrylate, acrylamide, methacrylamide, vinylidine
chloride, vinylidine bromide, vinyl esters, such as, vinyl acetate,
and vinyl propionate, dialkyl maleates or fumarates such as
dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl
fumarate, diethyl fumarate, and dibutyl fumarate. In one
embodiment, the third monomer is selected from methyl acrylate and
methyl methacrylate.
[0049] In one embodiment of a graft polymerization process to make
ABS, the process includes charging the reaction system with a
substrate such as diene rubber latex, adding a first portion of at
least one of a styrene and one of an acrylonitrile to the diene
rubber latex, adding to the reaction system, over a predetermined
time, a catalyst (or initiator) and a second portion of at least
one of acrylonitrile and styrene monomers, and polymerizing the
catalyzed reaction mixture of diene rubber latex, styrene and
acrylonitrile. The graft polymerization process may include an
emulsifier, which is a molecule with a hydrophobic end and a
hydrophillic end. As used herein, the term "substrate" refers to
the rubber latex backbone onto which the styrene and acrylonitrile
is grafted. In another embodiment, there is no pre-soak, or there
is no addition of the first portion of styrene and/or acrylonitrile
before the addition of the initiator.
[0050] In one embodiment, the substrate is a polybutadiene
emulsion, dispersed in water with an emulsifying agent, such a
fatty acid soap or a high molecular weight alkyl or alkaryl sulfate
or sulfonate. In another embodiment, the substrate may be
polybutadiene, styrene-butadiene rubber (SBR),
acrylonitile-butadiene rubber (NBR), homopolymers of chloroprene,
homopolymers of isoprene, copolymers of butadiene with isoprene, or
chloroprene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene,
1,2-propadiene, 1,4-pentadiene, 1,5-hexadiene, 1,2-pentadiene and
ABS. The substrate may be homogenized, unhomogenized, direct growth
or chemically or colloidally agglomerated. When the graft reaction
is carried out in semi-batch, batch, or continuous fashion, it is
desired to utilize a homonogenized substrate. Typically, the
average particle size of the substrate about 150 nanometers to
about 500 nanometers. If direct growth substrate is employed, the
particle size distribution is about 60 nanometers to about 500
nanometers.
[0051] The catalyst or initiator used in the graft reaction
includes peroxides and/or azo compounds which are active in
grafting and decompose into radicals. In addition to redox
initiators, peroxy initiators which have the capability to provide
free radicals to the reaction may also be used. Examples include
cumene hydroperoxide (CHP), sodium persulfate, potassium
persulfate, ammonium persulfate, di-isopropylbenzene hydroperoxide,
tertbutyl-peroxide, and 2-2'azo-bis-isobutyrylnitrile (AIBN), in
combination with other compounds such as reducing agents, heavy
metal salts and complexing agents. In one embodiment, the initiator
is cumene hydroperoxide in combination with a redox catalyst, such
as, Fe(II) with sugar or vanadium with sugar. Thermal initiators
should provide similar results if sufficient polymerization rates
can be obtained. A single initiator system or multiple initiator
additions over intervals of time can be employed. The initiator(s)
are added at various times including at the beginning of the
addition of the third monomer, during the addition of the third
monomer, at or after the completion of the addition of the third
monomer. If desired, one or more late addition monomers may be
employed.
[0052] In one embodiment, initiator is added to the reaction system
in an amount to provide sufficient initiator for the duration of
the polymerization reaction. In another embodiment, the initiator
or catalyst is included within the range of 0.01 to 2 percent by
weight of the polymerizable monomer. In a second embodiment,
initiator is added in an about of about 0.1 to 0.5 wt. % of the
polymerizable monomer. In yet another embodiment, initiator is
added during the addition of monomer formulation to ensure favoring
of the grafting reaction.
[0053] In alternate embodiments of the present invention, the
post-shot addition of the third monomer and/or initiator is delayed
until the conversion of styrene and acrylonitrile monomers is
greater than about 98% in one embodiment, or greater than 99% in
another embodiment, or greater than 99.5% in a further embodiment,
based on the original acrylonitrile monomer charged to the reaction
polymerization system.
[0054] Emulsifying agents which may be used in the graft
polymerization process include a fatty acid soap, an alkaline metal
or ammonium soap of a high molecular weight alkyl or alkaryl
sulfate or sulfonate, etc., in total amounts of about 0.1 to 8
parts by weight per 100 parts by weight of the monomer
formulation.
[0055] The afore-described process may be carried out in a batch,
semi-batch, or continuous operation. If in a semi-batch operation,
then an initial charge of substrate including water, surfactant and
polybutadiene is made to a reaction system and at or after the
completion of the initial charge, a pre-soak operation may be
carried out which include the addition of at least one of styrene,
acrylonitrile or a mixture of styrene and acrylonitrile. In one
embodiment, the temperature of the reaction system varies from
about 100.degree. F. to about 200.degree. F. In a second
embodiment, from about 120.degree. F.-180.degree. F. In a third
embodiment, from about 130.degree. F. to about 160.degree. F.
[0056] Sufficient heat removal is carried out as by the use of heat
exchangers so that the reaction system is maintained at a
satisfactory temperature to provide satisfactory polymerization.
Stirring is employed in the reaction system. The amount of stirring
and type is that amount and type which produces good dispersion of
the reactor contents and the desired amount of heat transfer.
[0057] Maintenance of the appropriate ratio of monovinylidene
aromatic hydrocarbon monomer to ethylenically unsaturated nitrile
monomer Applicants have also found that when the ratio of unreacted
styrene to acrylonitrile in the emulsion polymerization process is
kept at a ratio of greater than about 1.5 to 1, the final
compounded products are characterized with low yellowness by
keeping the reaction rich in styrene.
[0058] In one embodiment wherein a third monomer is to be added
late in the reaction, the ratio of total styrene monomer added to
acrylonitrile monomer added is about 1.5 to 1 to about 4 to 1, and
in another exemplary embodiment, about 2 to 1 to about 3.5 to
1.
[0059] In one embodiment, the ratio of total diene rubber added to
the total of styrene monomer and acrylonitrile monomer is about 0.1
to I to about 3.0 to 1, and in another exemplary embodiment, about
0.2 to 1 to about 2 to 1.
[0060] In still another embodiment, the post-shot addition of the
third monomer is delayed until the conversion of acrylonitrile is
greater than about 99% and the ratio of unreacted styrene to
unreacted acrylonitrile monomer is greater than about 4 for a final
product that is low in yellowness and residual monomers.
[0061] In one embodiment, at least one of acrylonitrile and styrene
monomers are added to the reaction system over a time of about 30
minutes to about 200 minutes. In another embodiment, at least one
of acrylonitrile and styrene monomers are added to the reaction
system over a time of about 45 minutes to about 160 minutes.
[0062] The ratio of the first portion of styrene monomer to the
second portion of styrene monomer is about 1 to 3 to about 1 to 5
and the ratio of a first portion of acrylonitrile monomer to the
second portion of acrylonitrile monomer is about 1 to 3 to about 1
to 5. In one embodiment, a first portion of at least one of styrene
monomer and acrylonitrile monomer or a mixture thereof is added to
the polybutadiene emulsion. In another embodiment, there is one
addition of styrene monomer and one addition of acrylonitrile
monomer.
[0063] In another embodiment, after permitting the reaction to
proceed for about 40 to 90 minutes after the addition of the
initiator, the acrylonitrile monomer, and the styrene monomer is
completed, about 0.5 to about 5.0 parts of a third monomer per 100
parts of total polymer and monomer, and/or additional initiator is
added to the reaction mixture.
[0064] Optimizing the rubber crosslink density of the substrate: As
previously noted, when a third monomer is added at 90-95%
conversion, good NAV reduction is achieved in the graft ABS
polymer, and surprisingly excellent results in NAV reduction is
achieved when the third monomer is added later on at 98 and 99% .
However, with the late addition of a third monomer, whether at 90%
plus or 99% plus, the impact properties of the ABS graft polymer
are poor. In the present invention, Applicants have found a method
of optimizing the impact of the ABS graft polymer, by optimizing
the rubber crosslink density of diene substrate, and selecting the
appropriate rubber crosslink density associated with the desired
room temperature and/or low temperature impact strength of the ABS
graft polymer (thus offsetting the low impact strength associated
with the late addition of a third monomer).
[0065] When this embodiment is employed along with the
afore-recited embodiments above, the addition of a third monomer
and lowering the crosslink density % A, the resultant product has a
low content of unreacted residual monomers along with a uniquely
improved impact strength.
[0066] In the present invention, a flow-impact balance in an ABS
graft polymer product is obtained while achieving higher conversion
and reduced monomer emissions, by offsetting the crosslink density
(% A) increase in the ABS graft polymer (due to increased
conversion) by selecting the diene substrate of lower crosslink
density (% A).
[0067] In one embodiment of the invention, the diene substrate has
a crosslink density of 20-60% A. In a second embodiment, it is
25-45% A. In yet another embodiment, an optimum product performance
is obtained with a crosslink density of 30-45% of the diene
substrate.
[0068] It should be noted that the emulsion polymerization reaction
of the present invention can be carried out in a batch process, a
semi-batch process, or a continuous process.
EXAMPLES
[0069] The invention will be further described by reference to the
following examples which are presented for the purpose of
illustration only and are not intended to limit the scope of the
invention.
[0070] Examples 1-13 are baseline runs, showing the preparation of
a high rubber ABS graft polymer by grafting polybutadiene with
styrene and acrylonitrile in accordance with an embodiment of the
present invention. Examples 1-13 were prepared according with the
following general procedure. An initial charge of a polybutadiene
emulsion was added to a three liter reaction vessel and heated to
57.2.degree. C. Next, 12.06 parts by weight of styrene were added
to the reaction vessel as a "pre-soak". After a pre-soak of about
20 minutes an addition of 0.375 parts of cumene hydroperoxide
initiator was started. The initiator was added to the reaction
vessel over a period of 70 minutes. Five minutes after starting the
initiator addition, a feed of 12.05 parts of acrylonitrile was
started. The acrylonitrile was added to the reaction vessel over a
period of 65 minutes. Ten minutes after the start of the initiator
addition, a feed of 24.09 parts of styrene was started. The styrene
was added to the reaction vessel over a period of 60 minutes.
[0071] In the baseline run with no late addition of a third
monomer, it is noted that the final product is high in NAVs.
[0072] Example 14 is a comparative example and was prepared similar
to the baseline runs of Examples 1-13 described above, except that
there was no addition of styrene to the polybutadiene emulsion
prior to the start of the initiator addition. Instead, the entire
amount of styrene, 36.15 parts, was feed into the reaction vessel
over a period of 60 minutes starting ten minutes after the start of
the initiator feed. Upon completion of the reaction, the reaction
product was analyzed for residual styrene and acrylonitrile
monomers and is shown in Table 1 below. Again, the run was high in
NAVs with more than 3500 parts per million (ppm) of styrene. The
results are follows:
1TABLE 1 Residual Residual Polybutadiene Styrene Acrylonitrile
EXAMPLE Emulsion (ppm) (ppm) 1 A* 4938 1303 2 A* 2497 2561 3 A*
4389 1031 4 A* 4683 1349 5 B** 5098 1533 6 B** 4892 679 7 B** 3388
1134 8 B** 3950 1046 9 B** 4004 861 10 B** 3538 1415 11 B** 3320
1305 12 B** 4285 1735 13 B** 3800 775 14 B** 6900 575 *Emulsion A
is an homogenized emulsion of polybutadiene having an average
particle size of 290 to 320 nanometers with a crosslink density of
56% A. **Emulsion B is an homogenized emulsion of polybutadiene
having an average particle size of 290 to 320 nanometers with a
crosslink density of 30-36% A.
[0073] Examples 15-31 show the preparation of ABS in accordance
with the late addition of a third monomer. In the examples,
polybutadiene is grafted with styrene and acrylonitrile in a
process that does not include a "pre-soak," but includes a
"post-shot" of a monomer that is reactive with styrene and
acrylonitrile. The examples were prepared according with the
following general procedure. An initial charge of a polybutadiene
emulsion B was added to a three liter reaction vessel and heated to
57.2.degree. C. Next, 0.475 parts of CHP initiator was added. The
initiator was added to the reaction vessel over a period of 70
minutes (Examples 15-27) or 85 minutes (Examples 28-31). The start
of the initiator is T=0. At T=0, a feed of acrylonitrile and a feed
of styrene were started. The acrylonitrile was added to the
reaction vessel over a period of 70 minutes (Examples 15-27) or 90
minutes (Examples 28-31). At a time of between T=110 minutes and
T=160 minutes a post-shot of initiator and a post shot of a monomer
is added to the reaction vessel over a period of 5 minutes. In
Examples 28 and 30, the post-shot of initiator and monomer was a
batch addition. See Table 2 for the amounts and the initiators and
added monomers for each example.
[0074] Upon completion of the reaction, the reaction product was
analyzed for residual styrene and acrylonitrile monomers. It is
desirable to have less than 3500 parts per million (ppm) of styrene
and less than 1500 ppm of acrylonitrile in the final product. It is
noted that the late addition of the third monomer in accordance to
the present invention (Post shot T of 135 and 160 minutes) gives
surprisingly lower residual styrene and acrylonitrile compared to
the earlier addition of the third monomer as in the prior art (Post
shot T of 110 minutes).
[0075] It should be noted that it appears that the lower post-shot
start time (T) yields lower residual monomer. For example, see
Examples 15 and 18, Examples 27 and 16, Examples 23 and 26, and
Examples 20 and 21.
2TABLE 2 Post- Post- Post- Post- Shot Post- Shot Residual Residual
AN Styrene PB Shot Shot Init. Shot Mon. Styrene AN Ex. (parts)
(parts) (parts) T= Init. (parts) Mon. (parts) (ppm) (ppm) 15 11.800
35.400 51.800 110 CHP 0.150 MMA 1.000 4214 168 16 11.300 33.900
51.800 160 CHP 0.250 MMA 3.000 1162 163 17 11.550 34.650 51.800 135
CHP 0.200 MMA 2.000 1809 519 18 11.800 35.400 51.800 160 CHP 0.150
MMA 1.000 2957 139 19 11.300 33.900 51.800 110 CHP 0.075 MMA 3.000
1337 204 20 11.300 33.900 51.800 110 CHP 0.150 MMA 3.000 1862 131
21 11.300 33.900 51.800 160 CHP 0.150 MMA 3.000 974 97 22 11.550
34.650 51.800 135 CHP 0.200 MMA 2.000 1806 120 23 11.800 35.400
51.800 110 CHP 0.250 MMA 1.000 3566 119 24 11.550 34.650 51.800 135
CHP 0.200 MMA 2.000 1168 147 25 11.800 35.400 51.800 160 CHP 0.250
MMA 1.000 5543 267 26 11.800 35.400 51.800 160 CHP 0.250 MMA 1.000
2596 48 27 11.300 33.900 51.800 110 CHP 0.250 MMA 3.000 1504 220 28
11.687 35.060 50.244 110 PPS 0.200 BA 3.000 660 693 29 11.687
35.060 50.244 110 CHP 0.200 BA 3.000 686 527 30 11.687 35.060
50.244 135 PPS 0.200 BA 3.000 756 527 31 11.687 35.060 50.244 160
CHP 0.200 BA 3.000 738 417 AN = aerylonitrile; PB = polybutadiene;
CHP = cumene hydroperoxide; PPS = potassium persulfate; MMA =
methymethacrylate; and BA = butylacrylate, Init. = initiator; Mon.
= monomer. T is time measured in minutes from first initiator
feed.
[0076] In the comparative base run Example 32, 50 parts of styrene
and acrylonitrile were added in a 3:1 ratio to an emulsion
containing 50 parts of polybutadiene. The emulsion polymerization
was initiated by-means of a CHP redox system using Fe(II) and
sugar. The monomers were fed into the emulsion over a period of 70
minutes but 12 parts of the styrene are added prior to the pumping
of the initiator and the remaining monomers. At the end of 70
minutes, the total solid was about 36% and styrene and
acrylonitrile levels were 3800 and 1500 ppm respectively.
[0077] In Examples 33-38 of the present invention, there was no
styrene presoak. The reaction was carried otherwise in the same
manner of semi-batch emulsion polymerization conditions. There was
a delay of 40 or 90 minutes (for post shot time of 110 or 160
minutes) until the addition of the methyl methacrylate monomer
(MMA) in conjunction with additional CHP initiator. It was noted
that for each case, either with 1 part MMA or 3, 0.15 or 0.25 parts
of CHP, total residual monomer was surprisingly less with late
addition time as compared to the base run.
3TABLE 3 Post Residual Residual Residual Total shot Parts Parts
Styrene AN MMA residual Ex. time MMA CHP (ppm) (ppm) (ppm) (ppm) 33
110 1 0.15 4214 168 248 4630 34 160 1 0.15 2957 139 451 3548 35 110
1 0.25 3566 119 288 3973 36 160 1 0.25 2596 48 458 3102 37 110 3
0.15 1862 131 788 2782 38 160 3 0.15 974 97 745 1816 39 110 3 0.25
1504 220 1246 2970 40 160 3 0.25 1162 163 953 2278
[0078] In Examples 41-47, polybutadiene was at 50 parts, the
styrene was 37 parts, and acrylonitrile 13 parts. Some of the
styrene was pre-soak, i.e., added to the polybutadiene prior to the
beginning of the polymerization with acrylonitrile.
[0079] Applicants have found that the best conversion is obtained
under the conditions with a pre-soak, and also extended time
delivery of the initiator, and that the lowest color materials
(most desirable in terms of low Yellowness Index) have the highest
ratio of unreacted styrene to acrylonitrile while the most colored
materials have substantial acrylonitrile. We also found that adding
the styrene in the pre-soak allows for higher conversion, but at
the expense of higher color.
4TABLE 4 styrene CHP CHP Styrene ppm ppm YI@ YI@ YI@ Examples
pre-soak parts pump/time feed/time AN styrene 400 F. 450 F. 500 F.
41 0 0.375 130 110 0 7633 24.8 25.7 26.2 42 0 0.375 100 90 373 5719
25.4 27.4 28.6 43 0 0.475 100 110 0 6849 25.8 26.3 26.8 44 7.5
0.425 115 100 412 4715 28.2 29.0 29.8 45 15 0.375 100 110 705 8314
28.4 28.9 29.9 46 15 0.375 130 90 1467 1693 29.8 30.8 31.5 47 15
0.475 100 90 930 2255 33.1 34.3 35.4
[0080] EXAMPLE 48. In this example, a design of experiments (DOE) 5
five factors (CHP level initially, styrene/acrylonitrile feed time,
CHP level in post-shot, methyl methacrylate level in post-shot,
timing of post-shot) was conducted for a total of 19 runs. A
statistical analysis of the Yellowness Index (YI) showed that the
YI is not impacted by the late addition of the third monomer, as
indicated below:
5 Term Coef StDev T P Constant 25.7837 0.1800 143.241 0.000 CHP
shot 0.2800 0.1962 1.427 0.174 Monomer feed time 0.3887 0.1962
1.982 0.066 MMA Loading -0.2450 0.1962 -1.249 0.231
[0081] As shown above, the statistically significant factor with
respect to the YI is from the monomer feed time, i.e., from the
maintenance of the appropriate ratio of unreacted styrene to
acrylonitrile.
[0082] EXAMPLE 49. In this example, butadiene substrates were made
by a batch process using 85/15 weight ratio of butadiene/styrene at
different crosslink density levels of % A, and then pressure
homogenized. Graft reactions were run on the homogenized substrates
at 51.3 parts rubber. Styrene monomers at 34 parts, acrylonitrile
at 11.7 parts and MMA at 3 parts were used for grafting. MMA was
added 30 minutes after the styrene and acrylonitrile charge was
completed. % A's were measured on the ABS graft polymer.
[0083] The results are as follows correlating the crosslink density
of the butadiene rubber and the product ABS graft polymer:
6 % A of substrate % A of HRG 21.6 56.9 30.3 60.4 42.1 64.1 51.8
69.4
[0084] EXAMPLE 50. The ABS graft polymers in Example 49 were
blended with SAN, compounded, and molded into bars for the notched
Izod impact measurement at room temperature. The results are as
follows.
7 % A of HRG Izod Impact (kJ/m2) 56.9 17.0 60.4 16.0 64.6 13.6 69.4
12.3
[0085] FIG. 1 and FIG. 2 are plots of data indicating the role that
the rubber crosslink density of diene rubber has in defining room
temperature and low temperature impact of ABS graft polymer. As
shown in FIG. 1, it has been discovered that the polybutadiene
substrate provides a baseline for the crosslink density of rubber
in ABS graft polymer. In FIG. 2, the room temperature notch Izod
impact strength is enhanced when substrate crosslink density of the
ABS graft polymer is lower. As a correlation, the notched Izod
impact strength is dependent on the rubber crosslink density of the
substrate.
[0086] FIG. 3 below shows the dependence of notched Izod impact at
-20.degree. C. on crosslink density (% A) of the rubber in an ABS
graft product, containing 70% polybutadiene rubber.
[0087] EXAMPLE 51. (30 runs total). A design of experiments (DOE)
of 2-level, four factor, full factorial response surface central
composite design (alpha of 1) was carried out according to the
factors and settings as shown in table below. Applicant's 30 runs,
including 6 repeats of the center point, showed the effect of
conversion and rubber crosslink density and to optimize the flow
and low temperature impact.
8TABLE 5 DOE Factors and Settings of Graft Reaction DOE Settings
Factor Factor Description Unit Low Medium High A Rubber Level in
ABS Parts* 60 65 70 Graft Polymer B Crosslink Density (% A) 28.3
39.8 54.8 of Substrate Used C Chain Transfer Agent Parts* 0.0 0.1
0.2 (TDDM) Used D Initial Temp of Reaction .degree. F. 134 140 146
*Parts = Parts per hundrcd parts of ABS graft polymer to be
formed
[0088] Water and the required amount of polybutadiene substrate (to
result in the desired rubber level in the ABS graft polymer
according to the settings chosen in the DOE) were charged to the
reactor. The crosslink density of the polybutadiene substrate was
changed from reaction to reaction according to the settings in the
DOE. After the batch is lined out at the initial temperature (which
varied from reaction to reaction according to the settings chosen
in the DOE), the redox system solutions of
FeSO.sub.4/Tetrasodiumpyrophosphate/Fructose were added. The
initiator (CHP), styrene monomer, acrylonitrile monomer, and chain
transfer agent (t-DDM) feed pumps were started, while the reactor
was maintained at the initial temperature specified in the DOE. The
styrene to acrylonitrile ratio was maintained at about 3 to 1. The
amounts varied from reaction to reaction such that the parts of
polybutadiene, styrene, acrylonitrile and methyl methacrylate added
up to a total of 100 parts. The monomer charges were completed in
about 45 minutes. When 50 minutes had elapsed after the start of
the monomer addition, 3 parts of methyl methacrylate were added
over a period of 5 minutes and another aliquot of CHP "post-shot"
was started at the same time and was charged over a period of 30
minutes. The reaction temperature was gradually raised by 8.degree.
F. in the first 40 minutes once the monomer charges began, and then
raised again to 160.degree. F. in the next 20 minutes, where it was
held constant for the next 60 minutes. The resulting ABS graft
polymer latex was aged for about 5 hours, and appropriate amount of
an anti-oxidant emulsion was added and aged again for another 3
hours. The latex was then coagulated with acid, and ABS graft
polymer was isolated and dried. Just before coagulation the latex
was tested for the content of residual monomers (NAVs). The dried
polymer was blended with styrene-acrylonitrile (SAN) polymer by
melt-mixing, molded into test bars and tested for notched Izod
impact.
[0089] FIG. 4 is representation of the results of the DOE, showing
the optimum crosslink density of rubber (% A) in the polybutadiene
substrate needed for low temperature (-20C) notched Izod impact,
while exhibiting low non-aqueous volatile (NAVs). As shown in the
Figure, an ABS graft polymer can be designed with non-aqueous
volatiles (NAVs) in desired levels, by choosing the substrate
appropriate crosslink density which meets impact requirements.
Thus, it is possible to maintain the flow-impact balance in an ABS
graft polymer but still be able to achieve higher conversion in a
ABS graft polymer polymerization process to reduce NAV and hence
reduce emissions. This is achieved by offsetting the % A increase
in ABS graft polymer (due to increased conversion) by selecting the
polybutadiene substrate of lower crosslink density (% A).
Example 50 (21 Runs)
[0090] In this example, a fractional factorial DOE (2.sup.(6-2)
plus center points) of 21 runs was conducted to determine the best
approach to control crosslink density. The DOE factors varied are
described below in Table 6.
9 Factor Description Units Low level Center pt. High Level A TFA
Soap pphm 1.50 2.00 2.50 charge level B Butadiene BD pphm 15.0
20.00 25.0 charge level C Initial CHP pphm/hr 0.0028 0.0098 0.0168
feed rate D Initiation .degree. F. 142 145 148 temperature E t-DDM
charge pphm 0.20 0.60 0.80 level F t-DDM feed pphm/hr 0 0.06 0.12
level pphm: parts per 100 parts of BD monomer
[0091] The initial charge of the reactor for the runs included: 150
parts water, 0.01 part ferrous sulfate FeSO4, 0.0039 EDTA; 0.4 part
tetra sodium pyrophosphate or TSPP; "E" parts of t-DDM as indicated
in the DOE factors table; "B" parts of butadiene charge level as
indicated in table above; and 0.050 parts of sodium formaldehyde
sulfoxalate dyhydrate SFS.
[0092] The feeds for the runs were as follows: "C" parts of initial
CHP for the 1.sup.st hour; 0.0882 parts of CHP until completion of
reaction at a rate of 0.0126 pphm (parts per 100 parts of monomer);
Butadiene monomer feed at a rate of 100-"B" in the table above,
spread over a period of 5 hr. reaction time; and "F" parts t-DDM,
spread over a period of 5 hr. reaction time.
[0093] The initiation temperature was at "D" with the polish
temperature (after the BD feed stops) of 160.degree. F.
[0094] The reaction procedure included first pulling a vacuum on
the reactor and then adding the initial charge of water,
FeSO.sub.4, ETDA, TFA soap, TSPP, initial TDDM, and the initial
butadiene monomer. The reaction mixture was heated to an initiation
temperature and then the SFS was added. The reaction mixture was
then mixed for five minutes and then the CHP feed was started. Ten
minutes after the start of the CHP feed the butadiene and the t-DDM
feeds were started. At the conclusion of the butadiene and t-DDM
feeds, the temperature of the reaction mixture was raised to the
polish temperature. The CHP feed was continued until a conversion
of between 93% to 96% was obtained and then the reaction mixture
was cooled to 150.degree. F. Any un-reacted butadiene was removed
by vacuum and then the resultant latex was homogenized to the
desired particle size. The results are as shown in Table 7.
10TABLE 7 Soap Level BD charge initial CHP Initiation tddm charge
tddm feed Run order pphm level pphm feed pphm/hr temp. .degree. F.
level pphm level pphm % A 1 2.5 25.0 0.0028 148 0.20 0.00 60.5 2
1.5 15.0 0.0028 148 0.20 0.60 18.4 3 2.0 20.0 0.0098 145 0.50 0.30
35.4 4 1.5 15.0 0.0168 142 0.80 0.60 13.7 5 2.5 15.0 0.0028 142
0.80 0.00 55.2 6 1.5 15.0 0.0028 142 0.20 0.00 62.0 7 1.5 25.0
0.0168 148 0.20 0.60 21.6 8 1.5 15.0 0.0168 148 0.80 0.00 55.1 9
1.5 25.0 0.0028 148 0.80 0.00 41.7 10 2.0 20.0 0.0098 145 0.50 0.30
35.0 11 1.5 25.0 0.0168 142 0.20 0.00 62.1 12 2.0 20.0 0.0098 145
0.50 0.30 35.3 13 2.5 25.0 0.0028 142 0.20 0.60 18.9 14 1.5 25.0
0.0028 142 0.80 0.60 9.1 15 2.0 20.0 0.0098 145 0.50 0.30 37.6 16
2.5 15.0 0.0028 148 0.80 0.60 17.0 17 2.0 20.0 0.0098 145 0.50 0.30
38.3 18 2.5 15.0 0.0168 148 0.20 0.00 64.7 19 2.5 15.0 0.0168 142
0.20 0.60 34.5 20 2.5 25.0 0.0168 142 0.80 0.00 52.3 21 2.5 25.0
0.0168 148 0.80 0.60 20.6
[0095] The DOE results as shown in FIG. 5 indicate that low
crosslink density polybutadiene substrate made with the semi-batch
process can be achieved by the continuous addition of t-DDM during
the butadiene feed portion of the reaction. Batch charging of t-DDM
is not effective at reducing the crosslink density below 49% . The
addition of t-DDM during the feed portion, instead of adding up
front at the beginning, is about 4 times more effective at reducing
the crosslink density. Therefore, similar crosslink density can be
achieved using lower amounts of t-DDM. The lower crosslink density
is beneficial when used in graft ABS reactions to achieve better
low temperature impact at high conversion.
[0096] While the invention has been described in terms of various
specific embodiments, those skilled in the art will recognize that
the invention can be practiced with modification within the spirit
and scope of the claims.
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